Liquid aqueous bleaching compositions

ABSTRACT

The present invention relates to a low viscosity, aqueous liquid composition suitable for bleaching and pretreating soiled fabrics. Such composition contains a peroxygen bleach, an ethoxylated nonionic surfactant, a zwitterionic betaine surfactant and a viscosity reducing agent. In addition to improved cleaning performance, such composition provides satisfactory fabric and color safety when used as a laundry pretreater.

TECHNICAL FIELD

The present invention relates to bleaching compositions particularlysuitable for the pretreatment of fabrics.

BACKGROUND OF THE INVENTION

Peroxygen bleach-containing compositions typically based on hydrogenperoxide have been extensively described in laundry applications aslaundry detergents, laundry additives or laundry pretreaters.

Indeed, it is known to use liquid aqueous bleaching compositionscomprising hydrogen peroxide in laundry pretreatment applications.Although, these liquid aqueous bleaching compositions provide somebleaching performance when used to pretreat a soiled fabric, there isstill some room for further improvement regarding the stains removalperformance on various stains including for example greasy stains aswell as for further improvement on bleaching performance in pretreatmentconditions, i.e. when the liquid aqueous composition is applied neat onthe fabric to bleach before the fabric is subsequently rinsed or washedthen rinsed with water.

Also such liquid aqueous compositions for laundry pretreatmentapplication should have water-like behaviour (low viscosity) forappropriate usage.

It is know that stain removal performance of liquid aqueous peroxygenbleach-containing compositions may be improved by the additions ofsurfactants. However, a problem encountered with the use of surfactantsystems in liquid aqueous peroxygen bleach-containing compositions isthat while providing effective stain removal performance to the fabricspretreated therewith, high viscosity is also delivered to thesecompositions.

Accordingly, the formulator of bleaching compositions suitable forlaundry pretreatment is faced with the challenge of formulating a liquidaqueous bleaching composition which exhibits effective stain removalperformance and bleaching performance as well as low viscosity. Thus, itis an object of the present invention to provide a liquid aqueouscomposition providing effective bleaching performance and effectivestain removal performance under laundry pretreatment conditions, whileexhibiting low-viscosity properties.

It has now been found that this object can be efficiently met byformulating a liquid aqueous composition comprising a peroxygen bleach,an ethoxylated nonionic surfactant (0.001%-30%), a zwitterionic betainesurfactant (0.001%-20%) and a viscosity controlling agent selected fromthe group consisting of C3-C6 alkyl ammonium salt, solvents, i.e.,glycols as defined herein, C3-C8 alcohols, and/or aromatic alcohols asdefined herein, and mixtures thereof.

It has now been found that such compositions when used to pretreatfabrics boosts the removal of various types of stains including greasystains and/or enzymatic stains and more surprisingly the bleachingperformance as compared to the stain removal and bleaching performancedelivered by the same compositions comprising only one of thesesurfactants (i.e., ethoxylated nonionic surfactant or zwitterionicbetaine surfactant) at equal total level of surfactant while deliveringlow viscosity. Indeed, it has been found that the addition of such aviscosity controlling agent allows to decrease the viscosity of a liquidaqueous peroxygen bleach-containing composition comprising anethoxylated nonionic surfactant and a zwitterionic betaine surfactantwithout compromising on the stain removal performance and bleachingperformance of the composition. In other words, it is by combining theseingredients that a liquid aqueous composition particularly suitable forpretreating fabrics, can be provided that combines optimum stain removaland bleaching performance as well as optimum viscosity characteristics.

Advantageously, the compositions of the present invention exhibiteffective stain removal performance on stains like kitchen soilscomprising mainly edible oils, bathroom soils comprising mainly sebumand/or soap scum, floor soils comprising mainly particulate soils andmore generally on any greasy stains (e.g., olive oil, mayonnaise,vegetal oil, make up like lipstick), enzymatic stains (grass, blood) aswell as bleachable stains (e.g., tea, coffee).

Advantageously, they also provide satisfactory fabric and colour safetywhen used as laundry pretreaters.

It has further surprisingly been found that the addition of C3-C6 alkylammonium salt and/or solvent as defined herein, in a liquid aqueousperoxygen bleach-containing composition comprising an ethoxylatednonionic surfactant and a zwitterionic betaine surfactant improves thephysical stability of these compositions upon prolonged periods ofstorage.

Advantageously, the addition of C3-C6 alkyl ammonium salts and/orsolvents as defined herein, in a liquid aqueous peroxygenbleach-containing composition comprising an ethoxylated nonionicsurfactant and a zwitterionic betaine surfactant improves therheological stability of such compositions. Indeed, the initialviscosity of the compositions herein is maintained constant (typicallydo not undergo more than 40%, preferably not more than 30%) when thesecompositions are used in a wide range of temperatures, typically from10° C. to 45° C. Also these compositions are clear in a broad range oftemperature, e.g. up to 45° C.

It is a further object of the present invention to provide such animproved liquid bleaching composition with low viscosity which is also aclear composition in a broad range of temperature, e.g. up to 45° C.

An advantage of the compositions of the present invention is that theyexhibit a great flexibility in the soils they may clean. Although thecompositions of the present invention are primarily formulated to beused as a laundry pretreater in its neat form, they may also be used inother laundry applications e.g., as a laundry detergent or a laundryadditive, or even in other household applications like in hard surfacecleaning applications. Accordingly, the compositions according to thepresent invention are able to perform in a variety of conditions, i.e.,in hard and soft water in diluted form.

SUMMARY OF THE INVENTION

The present invention encompasses a liquid aqueous composition having aviscosity of 1 cps to 100 cps when measured with a Brookfield viscometerat spindle 2, rpm 30 and 20° C. and comprising a peroxygen bleach, from0.001% to 30% by weight of the total composition of an ethoxylatednonionic surfactant, from 0.001% to 20% by weight of a zwitterionicbetaine surfactant and a viscosity controlling agent selected from thegroup consisting of:

C3-C6 alkyl ammonium salt,

glycol according to the formula:

R₁—O—(C_(x)—H_(2x))_(n)—R₂,

wherein R₁ is a saturated or unsaturated, substituted or unsubstituted,linear or branched alkyl group containing from 1 to 5 carbon atoms, R₂is hydrogen or a saturated or unsaturated, substituted or unsubstituted,linear or branched alkyl group containing from 1 to 5 carbon atoms, xranges from 2 to 4 and n ranges from 1 to 5;

an alcohol having the formula R_(a)—OH wherein R_(a) is a linear orbranched, saturated or unsaturated alkyl group containing from 3 to 8carbon atoms,

an aromatic alcohol according to the formula R_(b)—OH wherein R_(b) isan alkyl substituted or non-alkyl substituted aryl group containing from5 to 15 carbon atoms, and mixtures thereof.

The present invention further encompasses process of pretreating fabricswherein, the composition of the present invention is applied neat on thefabrics, and the fabrics are subsequently rinsed,or washed in a normalwash cycle and then rinsed with water.

DETAILED DESCRIPTION OF THE INVENTION The Liquid Cleaning Composition

The compositions according to the present invention are liquidcompositions as opposed to a solid or a gas. As used herein “liquid”includes “pasty” compositions. The liquid compositions herein areaqueous compositions.

Typically, the liquid aqueous compositions herein comprise from 10% to99.9% by weight of the total composition of water, preferably from 30%to 97%, even more preferably from 50% to 95% and more preferably from60% to 90%.

Typically, the liquid compositions according to the present inventionhave a pH up to 7, preferably from 1 to 6, and more preferably from 1.5to 5.5. Formulating the compositions according to the present inventionin the acidic pH range contributes to the chemical stability of thecompositions and to the stain removal performance of the compositions.The pH of the compositions may be adjusted by any acid or base known tothose skilled in the art. Examples of such agents are inorganic acidssuch as sulphuric acid and strong bases such as sodium hydroxide.

Peroxygen Bleach

As a first essential element the compositions according to the presentinvention comprise a peroxygen bleach or a mixture thereof. Indeed, thepresence of peroxygen bleach contributes to the excellent bleachingbenefits of said compositions. Suitable peroxygen bleaches for useherein are hydrogen peroxide, water soluble sources thereof, or mixturesthereof. As used herein a hydrogen peroxide source refers to anycompound which produces perhydroxyl ions when said compound is incontact with water.

Suitable water-soluble sources of hydrogen peroxide for use hereininclude percarbonates, persilicates, persulphates such asmonopersulfate, perborates, peroxyacids such as diperoxydodecandioicacid (DPDA), magnesium perphtalic acid, perlauric acid, perbenzoic andalkylperbenzoic acids, hydroperoxides, aliphatic and aromatic diacylperoxides, and mixtures thereof. Preferred peroxygen bleaches herein arehydrogen peroxide, hydroperoxide and/or diacyl peroxide. Hydrogenperoxide is the most preferred peroxygen bleach herein.

Suitable hydroperoxides for use herein are tert-butyl hydroperoxide,cumyl hydroperoxide, 2,4,4-trimethylpentyl-2-hydroperoxide,di-isopropylbenzene-monohydroperoxide, tert-amyl hydroperoxide and2,5-dimethyl-hexane-2,5-dihydroperoxide. Such hydroperoxides have theadvantage to be particularly safe to fabrics and colour while deliveringexcellent bleaching performance when used in any laundry application.

Suitable aliphatic diacyl peroxides for use herein are dilauroylperoxide, didecanoyl peroxide, dimyristoyl peroxide, or mixturesthereof. Suitable aromatic diacyl peroxide for use herein is for examplebenzoyl peroxide. Such diacyl peroxides have the advantage to beparticularly safe to fabrics and colour while delivering excellentbleaching performance when used in any laundry application.

Typically, the compositions herein comprise from 0.01% to 20% by weightof the total composition of said peroxygen bleach or mixtures thereof,preferably from 1% to 15% and more preferably from 2% to 10%.

Ethoxylated Nonionic Surfactant

As a second essential element the compositions according to the presentinvention comprise an ethoxylated nonionic surfactant or a mixturethereof at a level of from 0.001% to 30% by weight of the totalcomposition. Preferably, the compositions herein comprise from 0.01% to15% by weight of the total composition of said ethoxylated nonionicsurfactant or mixture thereof, more preferably from 0.5% to 10%, evenmore preferably from 0.5% to 9% and most preferably from 1% to 6%.

Suitable ethoxylated nonionic surfactants herein are ethoxylatednonionic surfactants according to the formula RO—(C₂H₄O)_(n)H, wherein Ris a C₆ to C₂₂ alkyl chain or a C₆ to C₂₈ alkyl benzene chain, andwherein n is from 0 to 20, preferably from 1 to 15 and, more preferablyfrom 2 to 15 and most preferably from 2 to 12. The preferred R chainsfor use herein are the C₈ to C₂₂ alkyl chains.

Preferred ethoxylated nonionic surfactants are according to the formulaabove and have an HLB (hydrophilic-lipophilic balance) below 16,preferably below 15, and more preferably below 14. Those ethoxylatednonionic surfactants have been found to provide good grease cuttingproperties.

Accordingly suitable ethoxylated nonionic surfactants for use herein areDobanol^(R) 91-2.5 (HLB=8.1; R is a mixture of C₉ and C₁₁ alkyl chains,n is 2.5), or Lutensol^(R) TO3 (HLB=8; R is a C₁₃ alkyl chains, n is 3),or Lutensol^(R) AO3 (HLB=8; R is a mixture of C₁₃ and C₁₅ alkyl chains,n is 3), or Tergitol^(R) 25L3 (HLB=7.7; R is in the range of C₁₂ to C₁₅alkyl chain length, n is 3), or Dobanol^(R) 23-3 (HLB=8.1; R is amixture of C₁₂ and C₁₃ alkyl chains, n is 3), or Dobanol^(R) 23-2(HLB=6.2; R is a mixture of C₁₂ and C₁₃ alkyl chains, n is 2), orDobanol^(R) 45-7 (HLB=11.6; R is a mixture of C₁₄ and C₁₅ alkyl chains,n is 7) Dobanol^(R) 23-6.5 (HLB=11.9; R is a mixture of C₁₂ and C₁₃alkyl chains, n is 6.5), or Dobanol^(R) 25-7 (HLB=12; R is a mixture ofC₁₂ and C₁₅ alkyl chains, n is 7), or Dobanol^(R) 91-5 (HLB=11.6; R is amixture of C₉ and C₁₁ alkyl chains, n is 5), or Dobanol^(R) 91-6(HLB=12.5; R is a mixture of C₉ and C₁₁ alkyl chains, n is 6), orDobanol^(R) 91-8 (HLB=13.7; R is a mixture of C₉ and C₁₁ alkyl chains, nis 8), Dobanol^(R) 91-10 (HLB=14.2; R is a mixture of C₉ to C₁₁ alkylchains, n is 10), or mixtures thereof. Preferred herein are Dobanol^(R)91-2.5, or Lutensol^(R) TO3, or Lutensol^(R) AO3, or Tergitol^(R) 25L3,or Dobanol^(R) 23-3, or Dobanol R^(R) 23-2, or mixtures thereof. TheseDobanol^(R) surfactants are commercially available from SHELL. TheseLutensol^(R) surfactants are commercially available from BASF and theseTergitol^(R) surfactants are commercially available from UNION CARBIDE.

Suitable chemical processes for preparing the ethoxylated nonionicsurfactants for use herein include condensation of correspondingalcohols with alkylene oxide, in the desired proportions. Such processesare well-known to the man skilled in the art and have been extensivelydescribed in the art.

The compositions herein may desirably comprise one of those ethoxylatednonionic surfactants or a mixture of those ethoxylated nonionicsurfactants having different HLBs (hydrophilic-lipophilic balance). In apreferred embodiment the compositions herein comprise an ethoxylatednonionic surfactant according to the above formula and having an HLB upto 10 (i.e., a so called hydrophobic ethoxylated nonionic surfactant),preferably below 10, more preferably below 9, and an ethoxylatednonionic surfactant according to the above formula and having an HLBabove 10 to 16 (i.e., a so called hydrophilic ethoxylated nonionicsurfactant), preferably from 11 to 14. Indeed, in this preferredembodiment the compositions of the present invention typically comprisefrom 0.01% to 15% by weight of the total composition of said hydrophobicethoxylated nonionic surfactant, preferably from 0.5% to 10% and from0.01% to 15% by weight of said hydrophilic ethoxylated nonionicsurfactant, preferably from 0.5% to 10%. Such mixtures of ethoxylatednonionic surfactants with different HLBs may be desired as they allowoptimum grease cleaning removal performance on a broader range of greasysoils having different hydrophobic/hydrophilic characters.

Zwitterionic Betaine Surfactants

As a third essential element the compositions according to the presentinvention comprise a zwitterionic betaine surfactant or a mixturethereof at a level of from 0.001% to 20% by weight of the totalcomposition. Preferably, the compositions herein comprise from 0.01% to10% by weight of the total composition of said zwitterionic betainesurfactant or mixture thereof, more preferably from 0.5% to 8% and mostpreferably from 1% to 5%.

Suitable zwitterionic betaine surfactants for use herein contain both acationic hydrophilic group, i.e., a quaternary ammonium group, andanionic hydrophilic group on the same molecule at a relatively widerange of pH's. The typical anionic hydrophilic groups are carboxylatesand sulfonates, although other groups like sulfates, phosphonates, andthe like can be used. A generic formula for the zwitterionic betainesurfactants to be used herein is:

R₁—N⁺(R₂)(R₃)R₄X⁻

wherein R₁ is a hydrophobic group; R₂ is hydrogen, C₁-C₆ alkyl, hydroxyalkyl or other substituted C₁-C₆ alkyl group; R₃ is C₁-C₆ alkyl, hydroxyalkyl or other substituted C₁-C₆ alkyl group which can also be joined toR₂ to form ring structures with the N, or a C₁-C₆ carboxylic acid groupor a C₁-C₆ sulfonate group; R₄ is a moiety joining the cationic nitrogenatom to the hydrophilic group and is typically an alkylene, hydroxyalkylene, or polyalkoxy group containing from 1 to 10 carbon atoms; andX is the hydrophilic group which is a carboxylate or sulfonate group.

Preferred hydrophobic groups R₁ are aliphatic or aromatic, saturated orunsaturated, substituted or unsubstituted hydrocarbon chains that cancontain linking groups such as amido groups, ester groups. Morepreferred R₁ is an alkyl group containing from 1 to 24 carbon atoms,preferably from 8 to 18, and more preferably from 10 to 16. These simplealkyl groups are preferred for cost and stability reasons. However, thehydrophobic group R₁ can also be an amido radical of the formulaR_(a)—C(O)—NH—(C(R_(b))₂)_(m), wherein R_(a) is an aliphatic oraromatic, saturated or unsaturated, substituted or unsubstitutedhydrocarbon chain, preferably an alkyl group containing from 8 up to 20carbon atoms, preferably up to 18, more preferably up to 16, R_(b) isselected from the group consisting of hydrogen and hydroxy groups, and mis from 1 to 4, preferably from 2 to 3, more preferably 3, with no morethan one hydroxy group in any (C(R_(b))₂) moiety.

Preferred R₂ is hydrogen, or a C₁-C₃ alkyl and more preferably methyl.Preferred R₃ is a C₁-C₄ carboxylic acid group or C1-C4 sulfonate group,or a C₁-C₃ alkyl and more preferably methyl. Preferred R₄ is (CH₂)_(n)wherein n is an integer from 1 to 10, preferably from 1 to 6, morepreferably is from 1 to 3.

Some common examples of betaine/sulphobetaine are described in U.S. Pat.Nos. 2,082,275, 2,702,279 and 2,255,082, incorporated herein byreference.

Examples of particularly suitable alkyldimethyl betaines includecoconut-dimethyl betaine, lauryl dimethyl betaine, decyl dimethylbetaine, 2-(N-decyl-N,N-dimethyl-ammonia)acetate, 2-(N-cocoN,N-dimethylammonio)acetate, myristyl dimethyl betaine, palmityldimethyl betaine, cetyl dimethyl betaine, stearyl dimethyl betaine. Forexample Coconut dimethyl betaine is commercially available from Seppicunder the trade name of Amonyl 265®. Lauryl betaine is commerciallyavailable from Albright & Wilson under the trade name Empigen BB/L®.

Examples of amidobetaines include cocoamidoethylbetaine, cocoamidopropylbetaine or C10-C14 fatty acylamidopropylene(hydropropylene)sulfobetaine.For example C10-C14 fatty acylamidopropylene(hydropropylene)sulfobetaineis commercially available from Sherex Company under the trade name“Varion CAS® sulfobetaine”.

A further example of betaine is Lauryl-immino-dipropionate commerciallyavailable from Rhone-Poulenc under the trade name Mirataine H2C-HA®.

Particularly preferred zwitterionic betaine surfactants for use hereinare salt free, i.e. that the zwitterionic betaine surfactant rawmaterial contains less than 5% by weight of salts, preferably less than2%, more preferably less than 1% and most preferably from 0.01% to 0.5%.

By “salts” is in meant herein any material having as base unit, a coupleof positive ion (or positive molecular ion) and negative ion (ornegative molecular ion) containing one or more halogen atoms. Such saltsinclude Sodium Chloride, Potassium Chloride, Sodium Bromide and thelike.

Such salts free zwitterionic betaine surfactants are obtainable byconventional manufacturing processes like inverse osmosis orfractionated precipitation. For example inverse osmosis is based on theprinciple of contacting the zwitterionic betaine surfactant raw material(commercially available ) with a polar solvent (it is to be understoodthat such a solvent is free of salts) separated by a semi-permeablemembrane for example acetate-cellulose. An adequate pressure is appliedon the system to allow the salts to migrate from the surfactant rawmaterial to the polar solvent phase. This way the zwitterionic betainesurfactant raw material is purified, i.e. the salts is subtracted fromthe raw material.

Advantageously, it has now been surprisingly found that the use of suchsalt free zwitterionic betaine surfactants delivers improved fabricsafety and/or colour safety when pretreating fabrics with a peroxygenbleach-containing composition comprising the same, as compared to theuse of the same zwitterionic betaine surfactants with higher amount ofsalts. Thus, in its broadest aspect, the present invention alsoencompasses the use of a composition comprising a salt free zwitterionicbetaine surfactant and a peroxygen bleach for pretreating fabrics (forbleaching fabrics in a process wherein the composition is applied, inits neat form onto the fabrics before rinsing them or washing and thenrinsing them with water) whereby colour safety is improved (i.e. colourdamage/decoloration is reduced) and/or fabric safety is improved.

The betaine zwitterionic surfactants herein have the ability to furtherboost the stain removal performance delivered by the ethoxylatednonionic surfactants herein on greasy stains, while providing improvedbleaching performance to the liquid peroxygen bleach-containingcompositions of the present invention comprising them.

Indeed, a significant cooperation has been observed between theseingredients to get optimum stain removal performance on a variety ofsoils, from particulate to non-particulate soils from hydrophobic tohydrophilic soils under any household application and especially laundryapplication on both hydrophilic and hydrophobic fabrics.

Optimum stain removal performance and bleaching performance are obtainedwhen the ethoxylated nonionic surfactant and the zwitterionic betainesurfactant are present in the compositions of the present inventioncomprising a peroxygen bleach (pH up to 7), at weight ratio of theethoxylated nonionic surfactant to the zwitterionic betaine surfactantof from 0.01 to 20, preferably from 0.1 to 15, more preferably from 0.5to 5 and most preferably from 0.8 to 3.

Advantageously, excellent stain removal performance and bleachingperformance can be obtained with the compositions herein at low totallevel of surfactants. Typically, the compositions herein comprise from0.01% to 20% by weight of the total composition of ethoxylated nonionicsurfactant and zwitterionic betaine surfactant, preferably from 0.1% to15%, more preferably from 0.5% to 10%, even more preferably below 10%and most preferably from 1% to 8%.

Indeed, the present invention is based on the finding that the use ofzwitterionic betaine surfactant on top of the ethoxylated nonionicsurfactant at the appropriate ratios, in a liquid aqueous compositioncomprising a peroxygen bleach (pH up to 7), boosts the bleachingperformance and the removal of various types of stains including greasystains (e.g., lipstick, olive oil, mayonnaise, vegetal oil, sebum,make-up), as compared to the bleaching and stain removal performancedelivered by the same composition based only on one of these surfactants(i.e., ethoxylated nonionic surfactant or zwitterionic betainesurfactant) at equal total level of surfactants. For example, it is onlyat very high levels of nonionic surfactants, as compared the total levelof ethoxylated nonionic surfactants and zwitterionic betaine surfactantspresent in the compositions of the present invention that similar greasecleaning benefit is observed.

The stain removal performance may be evaluated by the following testmethods on various type of stains.

A suitable test method for evaluating the stain removal performance on asoiled fabric under pretreatment condition is the following: Acomposition according to the present invention is applied neat to afabric preferably to the soiled portion of the fabric, left to act from1 to 10 minutes, and said pretreated fabric is then washed according tocommon washing conditions, at a temperature of from 30° to 70° C. forfrom 10 to 100 minutes. The stain removal is then evaluated by comparingside by side the soiled fabric pretreated with the composition of thepresent invention with those pretreated with the reference, e.g., thesame composition but comprising only an alkoxylated nonionic surfactantor only a zwitterionic betaine surfactant as the sole surfactant. Avisual grading may be used to assign difference in panel units (psu) ina range from 0 to 4.

The bleaching performance may be evaluated as for the stain removalperformance but the stains used are bleachable stains like coffee, teaand the like.

The Viscosity Controlling Agent

As a fourth essential element the compositions according to the presentinvention comprise a viscosity controlling agent.

The viscosity controlling agent suitable for use herein are selectedfrom the group consisting of:

C3-C6 alkyl ammonium salt,

glycol according to the formula:

R₁—O—(C_(x)—H_(2x))_(n)—R₂,

wherein R₁ is a saturated or unsaturated, substituted or unsubstituted,linear or branched alkyl group containing from 1 to 5 carbon atoms, R₂is hydrogen or a saturated or unsaturated, substituted or unsubstituted,linear or branched alkyl group containing from 1 to 5 carbon atoms, xranges from 2 to 4 and n ranges from 1 to 5;

an alcohol having the formula R_(a)—OH wherein R_(a) is a linear orbranched, saturated or unsaturated alkyl group containing from 3 to 8carbon atoms,

an aromatic alcohol according to the formula R_(b)—OH wherein R_(b) isan alkyl substituted or non-alkyl substituted aryl group containing from5 to 15 carbon atoms, and mixtures thereof.

Typically, the compositions herein comprises from 0.001% to 20% byweight of the total composition of such a viscosity controlling agent ormixture thereof, preferably from 0.001% to 10%, more preferably from0.01% to 10% and most preferably from 0.05% to 5%.

Suitable alkyl ammonium salts for use herein are ammonium salts ofbromide, chloride, iodide or sulphate containing from 3 to 6 carbonatoms, preferably from 4 to 5 carbon atoms. Example of such salts aretetra pentyl ammonium bromide and/or tetra-butyl ammonium bromide. Theyare both commercially available under their chemical name fromSigma-Aldrich or Flucka Chemicals.

Preferred glycols for use herein are according to the formula:

R₁—O—(C_(x)—H_(2x))_(n)—R₂,

wherein R₁ is a saturated or unsaturated, substituted or unsubstituted,linear or branched alkyl group containing from 2 to 4 carbon atoms, R₂is hydrogen or a saturated or unsaturated, substituted or unsubstituted,linear or branched alkyl group containing from 1 to 4 carbon atoms,preferably hydrogen or a C1-C4 alkyl group, more preferably hydrogen ormethyl, x ranges from 2 to 3, more preferably 2 and n ranges from 1 to3.

Examples of such glycols for use herein include DiEthylene Glycol ButylEther (also called Butyl Carbitol), DiEthylene Glycol methyl Butyl,DiPropilene Glycol Butyl Ether and/or DiPropilene Glycol methyl ButylEther. For example DiEthylene Glycol Butyl Ether may be commerciallyavailable from Fluka and Aldrich under its chemical name.

Preferred alcohols for use herein are those having the formula R_(a)—OHwherein R_(a) is a linear or branched, saturated or unsaturated alkylgroup containing from 3 to 8 carbon atoms, preferably from 4 to 8 andmore preferably from 4 to 7 or mixtures thereof.

Example of such alcohols include butanol, isobutanol, pentanol and/orisopentilic alcohol. Such alcohols may be commercially available fromFluka and Aldrich under their chemical name.

Preferred aromatic alcohols for used herein are those according to theformula R_(b)—OH wherein R_(b) is an alkyl substituted or non-alkylsubstituted aryl group containing from 5 to 15 carbon atoms, preferablyfrom 5 to 12, or mixtures thereof.

Examples of such aromatic alcohol include benzyl alcohol. Benzyl alcoholis commercially available from Fluka.

In a preferred embodiment herein optimum viscosity properties areobtained at a weigh ratio of the viscosity controlling agent to thezwitterionic betaine surfactant of 0.01 to 10, preferably of 0.1 to 1.0and more preferably of 0.2 to 0.5.

The viscosity of the compositions herein is from 1 cps to 100 cps,preferably from 5 cps to 80 cps, more preferably from 10 cps to 50 cpsand most preferably from 10 cps to 30 cps, when measured with aBrookfield Viscometer at spindle 2, rpm 30 and 20° C.

Importantly, in the present invention the improved stain removal benefitand bleaching benefit are delivered with a liquid composition which is awater-like, clear and transparent composition.

The appearance of a composition can be evaluated via turbidimetricanalysis. For example, the transparency of a composition can beevaluated by measuring its absorbency via a spectrophotometer at 800 nmwave length.

The viscosity controlling agents herein allow to deliver the requiredviscosity to the compositions herein. Not to be bound by theory, it isspeculated that the ammonium salts herein impacts on the electrostaticinteractions connecting the charged nonionic/zwitterionic micelles andthus reduce the viscosity of the compositions. Indeed, the nonionicsurfactants in the compositions herein are bound together with thezwitterionic betaine surfactants so as to forms charged micelles(thereby reducing the surfactant surface interface with the water phaseof the compositions herein). The charged micelles so formed interacttogether so as to form elongated structures, i.e., micelles connectedvia electrostatic interactions that results in increased viscosity. Alsothe presence of glycols, alcohols, and/or aromatic alcohols will competewith the zwitterionic betaine surfactants in order to form such micellesso as to make the resulting micelles less suitable to form elongatedstructures and hence to increase the viscosity of the compositions.

An advantage of the compositions of the present invention is that theyare physically and chemically stable upon prolonged periods of storage.

Chemical stability of the compositions herein may be evaluated bymeasuring the concentration of available oxygen (often abbreviated toAvO2) at given storage time after having manufactured the compositions.The concentration of available oxygen can be measured by chemicaltitration methods known in the art, such as the iodometric method,thiosulphatimetric method, the permanganometric method and thecerimetric method. Said methods and the criteria for the choice of theappropriate method are described for example in “Hydrogen Peroxide”, W.C. Schumb, C. N. Satterfield and R. L. Wentworth, Reinhold PublishingCorporation, New York, 1955 and “Organic Peroxides”, Daniel Swern,Editor Wiley Int. Science, 1970.

By “physically stable”, it is meant herein that no phase separationoccurs in the compositions for a period of 7 days at 50° C.

Optional Ingredients

The compositions herein may further comprise a variety of other optionalingredients such as chelating agents, builders, other surfactants,stabilisers, bleach activators, soil suspenders, soil suspendingpolyamine polymers, polymeric soil release agents, radical scavengers,catalysts, dye transfer agents, solvents, brighteners, perfumes,pigments and dyes.

Chelating Agents

Accordingly, the compositions of the present invention may comprise achelating agent as a preferred optional ingredient. Suitable chelatingagents may be any of those known to those skilled in the art such as theones selected from the group comprising phosphonate chelating agents,amino carboxylate chelating agents, other carboxylate chelating agents,polyfunctionally-substituted aromatic chelating agents, ethylenediamineN,N′-disuccinic acids, or mixtures thereof.

A chelating agent may be desired in the compositions of the presentinvention as it may contribute to reduce tensile strength loss offabrics and/or colour damage, when used in a laundry pretreatmentapplication. Indeed, the chelating agents inactivate the metal ionspresent on the surface of the fabrics and/or in the compositions thatotherwise would contribute to the radical decomposition of the peroxygenbleach.

Suitable phosphonate chelating agents for use herein may include alkalimetal ethane 1-hydroxy diphosphonates (HEDP), alkylene poly (alkylenephosphonate), as well as amino phosphonate compounds, including aminoaminotri(methylene phosphonic acid) (ATMP), nitrilo trimethylenephosphonates (NTP), ethylene diamine tetra methylene phosphonates, anddiethylene triamine penta methylene phosphonates (DTPMP). Thephosphonate compounds may be present either in their acid form or assalts of different cations on some or all of their acid functionalities.Preferred phosphonate chelating agents to be used herein are diethylenetriamine penta methylene phosphonate (DTPMP) and ethane 1-hydroxydiphosphonate (HEDP). Such phosphonate chelating agents are commerciallyavailable from Monsanto under the trade name DEQUEST®.

Polyfunctionally-substituted aromatic chelating agents may also beuseful in the compositions herein. See U.S. Pat. No. 3,812,044, issuedMay 21, 1974, to Connor et al. Preferred compounds of this type in acidform are dihydroxydisulfobenzenes such as1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelating agent for use herein is ethylenediamine N,N′-disuccinic acid, or alkali metal, or alkaline earth,ammonium or substitutes ammonium salts thereof or mixtures thereof.Ethylenediamine N,N′-disuccinic acids, especially the (S,S) isomer havebeen extensively described in U.S. Pat. No. 4,704,233, Nov. 3, 1987, toHartman and Perkins. Ethylenediamine N,N′-disuccinic acids is, forinstance, commercially available under the tradename ssEDDS® from PalmerResearch Laboratories.

Suitable amino carboxylates for use herein include ethylene diaminetetra acetates, diethylene triamine pentaacetates, diethylene triaminepentaacetate (DTPA), N-hydroxyethylethylenediamine triacetates,nitrilotriacetates, ethylenediamine tetrapropionates,triethylenetetraaminehexaacetates, ethanol-diglycines, propylene diaminetetracetic acid (PDTA) and methyl glycine di-acetic acid (MGDA), both intheir acid form, or in their alkali metal, ammonium, and substitutedammonium salt forms. Particularly suitable amino carboxylates to be usedherein are diethylene triamine penta acetic acid, propylene diaminetetracetic acid (PDTA) which is, for instance, commercially availablefrom BASF under the trade name Trilon FS® and methyl glycine di-aceticacid (MGDA).

Further carboxylate chelating agents for use herein include salicylicacid, aspartic acid, glutamic acid, glycine, malonic acid or mixturesthereof.

Another chelating agent for use herein is of the formula:

wherein R₁, R₂, R₃, and R₄ are independently selected from the groupconsisting of —H, alkyl, alkoxy, aryl, aryloxy, —Cl, —Br, —NO₂, —C(O)R′,and —SO₂R″; wherein R′ is selected from the group consisting of —H, —OH,alkyl, alkoxy, aryl, and aryloxy; R″ is selected from the groupconsisting of alkyl, alkoxy, aryl, and aryloxy; and R₅, R₆, R₇, and R₈are independently selected from the group consisting of —H and alkyl.

Particularly preferred chelating agents for use herein are aminoaminotri(methylene phosphonic acid), di-ethylene-triamino-pentaaceticacid, diethylene triamine penta methylene phosphonate, 1-hydroxy ethanediphosphonate, ethylenediamine N,N′-disuccinic acid, and mixturesthereof.

Typically, the compositions according to the present invention compriseup to 5% by weight of the total composition of a chelating agent, ormixtures thereof, preferably from 0.01% to 1.5% by weight and morepreferably from 0.01% to 0.5%.

Surfactants

The compositions of the present invention may further comprise othersurfactants than the ones mentioned hereinbefore including othernonionic surfactants, anionic surfactants, cationic surfactants and/oramphoteric surfactants.

Typically, the compositions according to the present invention maycomprise from 0.01% to 30% by weight of the total composition of anothersurfactant on top of the zwitterionic betaine surfactant and ethoxylatednonionic surfactant, preferably from 0.1% to 25% and more preferablyfrom 0.5% to 20%.

Suitable nonionic surfactants for use herein include polyhydroxy fattyacid amide surfactants, or mixtures thereof, according to the formula:

R²—C(O)—N(R¹)—Z,

wherein R¹ is H, or C₁-C₄ alkyl, C₁-C₄ hydrocarbyl, 2-hydroxy ethyl,2-hydroxy propyl or a mixture thereof, R² is C₅-C₃₁ hydrocarbyl, and Zis a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with atleast 3 hydroxyls directly connected to the chain, or an alkoxylatedderivative thereof.

Preferably, R¹ is C₁-C₄ alkyl, more preferably C₁ or C₂ alkyl and mostpreferably methyl, R² is a straight chain C₇-C₁ ₉ alkyl or alkenyl,preferably a straight chain C₉-C₁₈ alkyl or alkenyl, more preferably astraight chain C₁₁-C₁₈ alkyl or alkenyl, and most preferably a straightchain C₁₁-C₁₄ alkyl or alkenyl, or mixtures thereof. Z preferably willbe derived from a reducing sugar in a reductive amination reaction; morepreferably Z is a glycityl. Suitable reducing sugars include glucose,fructose, maltose, lactose, galactose, mannose and xylose. As rawmaterials, high dextrose corn syrup, high fructose corn syrup, and highmaltose corn syrup can be utilised as well as the individual sugarslisted above. These corn syrups may yield a mix of sugar components forZ. It should be understood that it is by no means intended to excludeother suitable raw materials. Z preferably will be selected from thegroup consisting of —CH₂—(CHOH)_(n)—CH₂OH,—CH(CH₂OH)—(CHOH)_(n−1)—CH₂OH, —CH₂—(CHOH)₂—(CHOR′)(CHOH)—CH₂OH, where nis an integer from 3 to 5, inclusive, and R′ is H or a cyclic oraliphatic monosaccharide, and alkoxylated derivatives thereof. Mostpreferred are glycityls wherein n is 4, particularly CH₂—(CHOH)₄—CH₂OH.

In formula R²—C(O)—N(R¹)—Z, R¹ can be, for example, N-methyl, N-ethyl,N-propyl, N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxypropyl. R²—C(O)—N< can be, for example, cocamide, stearamide, oleamide,lauramide, myristamide, capricamide, palmitamide, tallowamide and thelike. Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl,1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl,1-deoxymaltotriotityl and the like.

Suitable polyhydroxy fatty acid amide surfactants for use herein may becommercially available under the trade name HOE® from Hoechst.

Methods for making polyhydroxy fatty acid amide surfactants are known inthe art. In general, they can be made by reacting an alkyl amine with areducing sugar in a reductive amination reaction to form a correspondingN-alkyl polyhydroxyamine, and then reacting the N-alkyl polyhydroxyaminewith a fatty aliphatic ester or triglyceride in a condensation/amidationstep to form the N-alkyl, N-polyhydroxy fatty acid amide product.Processes for making compositions containing polyhydroxy fatty acidamides are disclosed for example in GB patent specification 809,060,published Feb. 18, 1959, by Thomas Hedley & Co., Ltd., U.S. Pat. No.2,965,576, issued Dec. 20, 1960 to E. R. Wilson, U.S. Pat. No.2,703,798, Anthony M. Schwartz, issued Mar. 8, 1955, U.S. Pat. No.1,985,424, issued Dec. 25, 1934 to Piggott and WO92/06070, each of whichis incorporated herein by reference.

Suitable anionic surfactants for use in the compositions herein includewater-soluble salts or acids of the formula ROSO₃M wherein R preferablyis a C₁₀-C₂₄ hydrocarbyl, preferably an alkyl or hydroxyalkyl having aC₁₀-C₂₀ alkyl component, more preferably a C₁₂-C₁₈ alkyl orhydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation(e.g., sodium, potassium, lithium), or ammonium or substituted ammonium(e.g., methyl-, dimethyl-, and trimethyl ammonium cations and quaternaryammonium cations, such as tetramethyl-ammonium and dimethyl piperdiniumcations and quaternary ammonium cations derived from alkylamines such asethylamine, diethylamine, triethylamine, and mixtures thereof, and thelike). Typically, alkyl chains of C₁₂₋₁₆ are preferred for lower washtemperatures (e.g., below about 50° C.) and C₁₆₋₁₈ alkyl chains arepreferred for higher wash temperatures (e.g., above about 50° C.).

Other suitable anionic surfactants for use herein are water-solublesalts or acids of the formula RO(A)_(m)SO₃M wherein R is anunsubstituted C₁₀-C₂₄ alkyl or hydroxyalkyl group having a C₁₀-C₂₄ alkylcomponent, preferably a C₁₂-C₂₀ alkyl or hydroxyalkyl, more preferablyC₁₂-C₁₈ alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m isgreater than zero, typically between about 0.5 and about 6, morepreferably between about 0.5 and about 3, and M is H or a cation whichcan be, for example, a metal cation (e.g., sodium, potassium, lithium,calcium, magnesium, etc.), ammonium or substituted-ammonium cation.Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates arecontemplated herein. Specific examples of substituted ammonium cationsinclude methyl-, dimethyl-, trimethyl-ammonium and quaternary ammoniumcations, such as tetramethyl-ammonium, dimethyl piperdinium and cationsderived from alkanolamines such as ethylamine, diethylamine,triethylamine, mixtures thereof, and the like. Exemplary surfactants areC₁₂-C₁₈ alkyl polyethoxylate (1.0) sulfate, C₁₂-C₁₈E(1.0)M), C₁₂-C₁₈alkyl polyethoxylate (2.25) sulfate, C₁₂-C₁₈E(2.25)M), C₁₂-C₁₈ alkylpolyethoxylate (3.0) sulfate C₁₂-C₁₈E(3.0), and C₁₂-C₁₈ alkylpolyethoxylate (4.0) sulfate C₁₂-C₁₈E(4.0)M), wherein M is convenientlyselected from sodium and potassium.

Other anionic surfactants useful for detersive purposes can also be usedherein. These can include salts (including, for example, sodium,potassium, ammonium, and substituted ammonium salts such as mono-, di-and triethanolamine salts) of soap, C₉-C₂₀ linearalkylbenzenesulfonates, C₈-C₂₂ primary or secondary alkanesulfonates,C₈-C₂₄ olefinsulfonates, sulfonated polycarboxylic acids prepared bysulfonation of the pyrolyzed product of alkaline earth metal citrates,e.g., as described in British patent specification No. 1,082,179, C₈-C₂₄alkylpolyglycolethersulfates (containing up to 10 moles of ethyleneoxide); alkyl ester sulfonates such as C₁₄₋₁₆ methyl ester sulfonates;acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenolethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates,isethionates such as the acyl isethionates, N-acyl taurates, alkylsuccinamates and sulfosuccinates, monoesters of sulfosuccinate(especially saturated and unsaturated C₁₂-C₁₈ monoesters) diesters ofsulfosuccinate (especially saturated and unsaturated C₆-C₁₄ diesters),sulfates of alkylpolysaccharides such as the sulfates ofalkylpolyglucoside (the nonionic nonsulfated compounds being describedbelow), branched primary alkyl sulfates, alkyl polyethoxy carboxylatessuch as those of the formula RO(CH₂CH₂O)_(k)CH₂COO—M⁺ wherein R is aC₈-C₂₂ alkyl, k is an integer from 0 to 10, and M is a solublesalt-forming cation. Resin acids and hydrogenated resin acids are alsosuitable, such as rosin, hydrogenated rosin, and resin acids andhydrogenated resin acids present in or derived from tall oil. Furtherexamples are given in “Surface Active Agents and Detergents” (Vol. I andII by Schwartz, Perry and Berch). A variety of such surfactants are alsogenerally disclosed in U.S. Pat. No. 3,929,678, issued Dec. 30, 1975, toLaughlin, et al. at Column 23, line 58 through Column 29, line 23(herein incorporated by reference).

Other suitable anionic surfactants for use herein also include acylsarcosinate or mixtures thereof, in its acid and/or salt form,preferably long chain acyl sarcosinates having the following formula:

wherein M is hydrogen or a cationic moiety and wherein R is an alkylgroup of from 11 to 15 carbon atoms, preferably of from 11 to 13 carbonatoms. Preferred M are hydrogen and alkali metal salts, especiallysodium and potassium. Said acyl sarcosinate surfactants are derived fromnatural fatty acids and the amino-acid sarcosine (N-methyl glycine).They are suitable to be used as aqueous solution of their salt or intheir acidic form as powder. Being derivatives of natural fatty acids,said acyl sarcosinates are rapidly and completely biodegradable and havegood skin compatibility.

Accordingly, suitable long chain acyl sarcosinates to be used hereininclude C₁₂ acyl sarcosinate (i.e., an acyl sarcosinate according to theabove formula wherein M is hydrogen and R is an alkyl group of 11 carbonatoms) and C₁₄ acyl sarcosinate (i.e., an acyl sarcosinate according tothe above formula wherein M is hydrogen and R is an alkyl group of 13carbon atoms). C₁₂ acyl sarcosinate is commercially available, forexample, as Hamposyl L-30® supplied by Hampshire. C₁₄ acyl sarcosinateis commercially available, for example, as Hamposyl M-30® supplied byHampshire.

Suitable amphoteric surfactants for use herein include amine oxideshaving the following formula R₁R₂R₃NO wherein each of R1, R2 and R3 isindependently a saturated substituted or unsubstituted, linear orbranched hydrocarbon chains of from 1 to 30 carbon atoms. Preferredamine oxide surfactants to be used according to the present inventionare amine oxides having the following formula R₁R₂R₃NO wherein R1 is anhydrocarbon chain comprising from 1 to 30 carbon atoms, preferably from6 to 20, more preferably from 8 to 16, most preferably from 8 to 12, andwherein R2 and R3 are independently substituted or unsubstituted, linearor branched hydrocarbon chains comprising from 1 to 4 carbon atoms,preferably from 1 to 3 carbon atoms, and more preferably are methylgroups. R1 may be a saturated substituted or unsubstituted linear orbranched hydrocarbon chain. Suitable amine oxides for use herein are forinstance natural blend C8-C10 amine oxides as well as C12-C16 amineoxides commercially available from Hoechst.

Radical Scavengers

The compositions of the present invention may comprise a radicalscavenger or a mixture thereof. Suitable radical scavengers for useherein include the well-known substituted mono and dihydroxy benzenesand their analogs, alkyl and aryl carboxylates and mixtures thereof.Preferred such radical scavengers for use herein include di-tert-butylhydroxy toluene (BHT), hydroquinone, di-tert-butyl hydroquinone,mono-tert-butyl hydroquinone, tert-butyl-hydroxy anysole, benzoic acid,toluic acid, catechol, t-butyl catechol, benzylamine,1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl) butane, n-propyl-gallateor mixtures thereof and highly preferred is di-tert-butyl hydroxytoluene. Such radical scavengers like N-propyl-gallate may becommercially available from Nipa Laboratories under the trade nameNipanox S1®. Radical scavengers when used, are typically present hereinin amounts ranging up to 10% by weight of the total composition andpreferably from 0.001% to 0.5% by weight.

The presence of radical scavengers may contribute to reduce tensilestrength loss of fabrics and/or colour damage when the compositions ofthe present invention are used in a laundry pretreatment application.

Antioxidants

The compositions according to the present invention may further comprisean antioxidant or mixtures thereof. Typically, the compositions hereincomprise up to 10% by weight of the total composition of an antioxidantor mixtures thereof, preferably from 0.002% to 5%, more preferably from0.005% to 2%, and most preferably from 0.01% to 1%.

Suitable antioxidants for use herein include organic acids like citricacid, ascorbic acid, tartaric acid, adipic acid and sorbic acid, oramines like lecithin, or aminoacids like glutamine, methionine andcysteine, or esters like ascorbil palmitate, ascorbil stearate andtriethylcitrate, or mixtures thereof. Preferred antioxidants for useherein are citric acid, ascorbic acid, ascorbil palmitate, lecithin ormixtures thereof.

Bleach Activators

As an optional ingredient, the compositions of the present invention maycomprise a bleach activator or mixtures thereof. By “bleach activator”,it is meant herein a compound which reacts with hydrogen peroxide toform a peracid. The peracid thus formed constitutes the activatedbleach. Suitable bleach activators to be used herein include thosebelonging to the class of esters, amides, imides, or anhydrides.Examples of suitable compounds of this type are disclosed in BritishPatent GB 1 586 769 and GB 2 143 231 and a method for their formationinto a prilled form is described in European Published PatentApplication EP-A-62 523. Suitable examples of such compounds to be usedherein are tetracetyl ethylene diamine (TAED), sodium 3,5,5 trimethylhexanoyloxybenzene sulphonate, diperoxy dodecanoic acid as described forinstance in U.S. Pat. No. 4,818,425 and nonylamide of peroxyadipic acidas described for instance in U.S. Pat. No. 4,259,201 andn-nonanoyloxybenzenesulphonate (NOBS). Also suitable are N-acylcaprolactams selected from the group consisting of substituted orunsubstituted benzoyl caprolactam, octanoyl caprolactam, nonanoylcaprolactam, hexanoyl caprolactam, decanoyl caprolactam, undecenoylcaprolactam, formyl caprolactam, acetyl caprolactam, propanoylcaprolactam, butanoyl caprolactam pentanoyl caprolactam or mixturesthereof. A particular family of bleach activators of interest wasdisclosed in EP 624 154, and particularly preferred in that family isacetyl triethyl citrate (ATC). Acetyl triethyl citrate has the advantagethat it is environmental-friendly as it eventually degrades into citricacid and alcohol. Furthermore, acetyl triethyl citrate has a goodhydrolytical stability in the product upon storage and it is anefficient bleach activator. Finally, it provides good building capacityto the composition. The compositions according to the present inventionmay comprise from 0.01% to 20% by weight of the total composition ofsaid bleach activator, or mixtures thereof, preferably from 1% to 10%,and more preferably from 3% to 7%

Process of Pretreating Fabrics

In the present invention, the liquid aqueous composition of the presentinvention is applied neat onto at least a portion of a soiled fabric,optionally left to act onto said fabric, typically for a period of timeof a few seconds to several hours, before the fabric is rinsed, orwashed then rinsed.

In this mode, the neat compositions can optionally be left to act ontosaid fabrics for a period of time ranging from 10 seconds to 1 hour,preferably 1 minute to 15 minutes, more preferably 1 minute to 5 minutesbefore the fabrics are rinsed, or washed then rinsed, provided that thecomposition is not left to dry onto said fabrics. For particularlythough stains, it may be appropriate to further rub or brush saidfabrics by means of a sponge or a brush, or by rubbing two pieces offabrics against each other.

By “washing”, it is to be understood herein that the fabrics arecontacted with a conventional detergent composition comprising at leastone surface active agent in an aqueous bath, this washing may occur bymeans of a washing machine or simply by hands.

By “in its neat form”, it is to be understood that the liquidcompositions are applied directly onto the fabrics to be pretreatedwithout undergoing any dilution, i.e. the liquid aqueous compositionsherein are applied onto the fabrics as described herein.

According to the process of pretreating soiled fabrics of the presentinvention, the liquid aqueous compositions herein should preferably notbe left to dry onto the fabrics. It has been found that waterevaporation contributes to increase the concentration of free radicalsonto the surface of the fabrics and, consequently, the rate of chainreaction. It is also speculated that an auto-oxidation reaction occursupon evaporation of water when the liquid compositions are left to dryonto the fabrics. Said reaction of auto-oxidation generatesperoxy-radicals which may contribute to the degradation of cellulose.Thus, not leaving the liquid compositions, as described herein, to dryonto the fabrics, in a process of pretreating soiled fabrics,contributes to reduce the tensile strength loss and/or colour damagewhen pretreating fabrics with liquid peroxygen bleach-containingcompositions.

The compositions herein may also be used in a “soaking mode” where acomposition, as defined herein, is first diluted in an aqueous bath andthe fabrics are immersed and soaked in the bath, before they are rinsed,or in a “through the wash mode”, where a composition, as defined herein,is added on top of a wash liquor formed by dissolution or dispersion ofa typical laundry detergent. It is also essential in both cases, thatthe fabrics be rinsed after they have been contacted with saidcomposition, before said composition has completely dried off.

Depending on the end-use envisioned, the compositions herein can bepackaged in a variety of containers including conventional bottles,bottles equipped with roll-on, sponge, brusher or sprayers.

The invention is further illustrated by the following examples.

EXAMPLES

Following compositions were made by mixing the listed ingredients in thelisted proportions (weight % unless otherwise specified).

Compositions I II III IV V VI VII VIII Dobanol ® 45-7 1.6 2.0 1.6 1.61.6 1.6 2.6 2.6 Dobanol ® 23-3 2.0 2.0 2.0 2.0 2.0 2.0 1.0 1.0 LaurylBetaine — — 2.4 2.4 2.4 2.4 2.4 2.4 Mirataine H2C-HA ® 5.0 2.4 — — — — —— H₂O₂ 7.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 TPAB 1.0 0.75 0.5 — — — — — DPGBE0.5 — — 1.0 0.75 — — — DEGBE — — — — — 1.0 0.5 — Benzilic alcohol — — —— — — — 0.5 HEDP 0.16 — 0.16 0.16 — 0.16 0.16 0.16 DTPMP — 0.18 — — 0.18— — — Propyl gallate 0.1 0.1 0.1 0.1 0.3 0.1 0.1 0.1 Citric acid 0.050.05 0.05 0.05 0.05 0.05 0.05 0.05 Water and minors up to 100% H2SO4 upto pH 4 or 5 10 25 33 38 47 37 30 42 Initial Viscosity in cps TPAB isTetra Pentyl Ammonium Bromide. DPGBE is Di Propylene Glycol Butyl Ether.DEGBE is Di Ethylene Glycol Butyl Ether. HEDP is 1-hydroxy-ethanediphosphonate. DTPMP is diethylene triamine penta methylene phosphonate.Mirataine H2C-Ha ® is Lauryl-immino-dipropionate. Dobanol ® 23-3 is aC12—C13 E03 nonionic surfactant commercially available from SHELL.Dobanol ® 45-7 is a C14—C15 E07 nonionic surfactant commerciallyavailable from SHELL. Initial viscosity it is meant herein the viscosityof the product freshly made measured by using a Brookfield DigitalViscometer Model DV-II with spindle number 2 at 20° C.

TPAB is Tetra Pentyl Ammonium Bromide.

DPGBE is Di Propylen Glycol Butyl Ether.

DEGBE is Di Ethylen Glycol Butyl Ether.

HEDP is 1-hydroxy-ethane diphosphonate.

DTPMP is diethylene triamine penta methylene phosphonate.

Mirataine H2C-HA® is Lauryl-immino-dipropionate.

Dobanol® 23-3 is a C12-C13 EO3 nonionic surfactant commerciallyavailable from SHELL.

Dobanol® 45-7 is a C14-C15 EO7 nonionic surfactant commerciallyavailable from SHELL.

Initial viscosity it is meant herein the viscosity of the productfreshly made measured by using a Brookfield Digital Viscometer ModelDV-III with spindle number 2 at 20° C.

Compositions IX X XI XII XIII XIV XV XVI Dobanol ® 91-10 — — — 1.6 — —1.6 — Dobanol ® 45-7 — 2.0 1.6 — 2.6 1.6 — 2.0 Dobanol ® 23-3 — — 2.02.0 1.0 2.0 2.0 — Salt-free Betaine* 5.0 2.4 2.4 2.4 2.4 5.0 5.0 5.0H₂O₂ 7.0 7.0 6.0 7.0 5.8 7.0 7.0 7.0 HEDP 0.16 — 0.16 — 0.16 0.16 0.160.16 DTPMP — 0.18 — 0.18 — — — — Propylgallate 0.1 0.1 — — — 0.1 0.1 0.1BHT — — 0.1 0.1 0.1 — — — TPAB 1.0 0.75 0.5 — — — — — DPGBE 0.5 — — 1.00.75 — — — DEGBE — — — — — 1.0 0.5 — Benzilic alcohol — — — — — — — 0.5Citric acid 0.05 0.05 0.50 0.05 0.50 0.05 0.05 0.05 Water and minors upto 100% H2SO4 up to pH 4 or 5 Initial Viscosity 10 25 3 38 47 37 30 42in cps HEDP is 1-hydroxy-ethane diphosphonate. DTPMP is diethylenetriamine penta methylene phosphonate. BHT is di-tert-butyl hydroxytoluene Salt-free Betaine* is Lauryl di-methyl betaine containing 0.3%by weight of sodium chloride. This betaine is obtained by purificationfrom commercially available Lauryl di-methyl betaine GENAGEN LAB ®(Hoechst)(which contains 7.5% by weight of sodium chloride).

HEDP is 1-hydroxy-ethane diphosphonate.

DTPMP is diethylene triamine penta methylene phosphonate.

BHT is di-tert-butyl hydroxy toluene

Salt-free Betaine* is Lauryl di-methyl betaine containing 0.3% by weightof sodium chloride. This betaine is obtained by purification fromcommercially available Lauryl di-methyl betaine GENAGEN LAB®(Hoechst)(which contains 7.5% by weight of sodium chloride).

Compositions I to XVI when used to pretreat soiled fabrics exhibitexcellent overall stain removal performance especially on greasy stainslike lipstick, make-up, olive oil, mayonnaise, sebum and the like, andimproved bleaching performance.

In the pretreatment mode, any of the compositions I to XVI is appliedneat on the stained portion of a fabric and left to act thereon for 5minutes. Then the fabric is washed with a conventional detergent andrinsed.

What is claimed is:
 1. A aqueous liquid bleaching compositioncomprising: a) from 0.0% to 20% by weight, of a peroxygen bleach; b)from 0.001% to 20% by weight, of a zwitterionic betaine surfactant andfrom 0.001% to 30% by weight, of an ethoxylated nonionic surfactant; c)from 0.001% to 20% by weight, of a viscosity controlling agent selectedfrom the group consisting of i. C₃-C₆ alkyl ammonium salts; ii. a glycolhaving the formula R₁—O—(C_(x)H_(2x))_(n)—R₂, wherein R₁ is C₁-C₅saturated or unsaturated, substituted or unsubstituted alkyl; R₂ ishydrogen, C₁-C₅ saturated or unsaturated, substituted or unsubstitutedalkyl, and mixtures thereof, x has a value from 2 to 4; n has a valuefrom 1 to 5; iii. an alcohol having the formula R_(a)—OH wherein R_(a)is C₃-C₈ saturated or unsaturated, substituted or unsubstituted alkyl;iv. an alcohol having the formula R_(b)—OH wherein R_(b) is C₅-C₁₅ alkylsubstituted or non-alkyl substituted aryl; and v. mixtures thereof; andd) the balance carrier and adjunct ingredients; wherein said compositionhas a viscosity of from cps to 100 cps when measured with a Brookfieldviscometer with spindle 2, at 30 rpm and 20° C.
 2. A compositionaccording to claim 1 further comprising from 0.01% to 15% by weight, ofa nonionic surfactant having the formula: RO—(C₂H₄O)_(n)H wherein R isC₆-C₂₂ alkyl, C₆-C₂₈ alkyl benzene, and mixtures thereof; n is from to20.
 3. A composition according to claim 2 comprising from 0.5% to 10% byweight, of said surfactant.
 4. A composition according to claim 3comprising from 1% to 6% by weight, of said surfactant.
 5. A compositionaccording to claim 1 wherein said zwitterionic betaine surfactant hasthe formula:

wherein R₁ has the formula:

R_(a) is C₈-C₂₀ saturated or unsaturated aliphatic, C₈-C₂₀ substitutedor unsubstituted aliphatic, C₈-C₂₀ substituted or unsubstitutedaromatic; and mixtures thereof; R_(b) is hydrogen, hydroxyl, or mixturesthereof; m is from 1 to 4; R₂ and R₃ are each independently hydrogen,C₁-C₆ alkyl, C₁-C₆ substituted alkyl, C₁-C₆ hydroxy alkyl, C₁-C₆sulfonate, and mixtures thereof; or R₂ and R₃ can be taken together toform a ring which includes the N atom; R₄ is C₁-C₁₀ alkylene, C₁-C₁₀hydroxy alkylene, C₁-C₁₀ polyalkyleneoxy, and mixtures thereof; X iscarboxylate, sulfonate, and mixtures thereof.
 6. A composition accordingto claim 5 wherein said zwitterionic betaine surfactant comprises lessthan 3% by weight, of salt.
 7. A composition according to claim 6wherein said surfactant comprises less than 2% by weight, of salt.
 8. Acomposition according to claim 7 wherein said surfactant comprises lessthan 1% by weight, of salt.
 9. A composition according to claim 8wherein said surfactant comprises from 0.01% to 0.5% by weight, of salt.10. A composition according to claim 5 comprising from 0.5% to 8% byweight, of said zwitterionic betaine surfactant.
 11. A compositionaccording to claim 10 comprising from 1% to 5% by weight, of saidzwitterionic betaine surfactant.
 12. A composition according to claim 1wherein said composition comprises from 1% to 15% by weight, of saidperoxygen bleach.
 13. A composition according to claim 12 wherein saidcomposition comprises from 2% to 10% by weight, of said peroxygenbleach.
 14. A composition according to claim 1 wherein said peroxygenbleach is hydrogen peroxide or a source of hydrogen peroxide selectedfrom the group consisting of percarbonates, persilicates, persulphates,peroxyacids, hydroperoxides, diacyl peroxides, and mixtures thereof. 15.A composition according to claim 14 wherein said hydroperoxides areselected from the group consisting of tert-butyl hydroperoxide, cumylhydroperoxide, 2,4,4-trimethylpentyl-2-hydroperoxide,di-isopropylbenzene monohydroperoxide, tert-amyl hydroperoxide, and2,5-dimethyl hexane-2,5-dihydorperoxide.
 16. A composition according toclaim 14 wherein said diacyl peroxide is selected from the groupconsisting of dilauroyl peroxide, didecanoyl peroxide, dimyristoylperoxide, and mixtures thereof.
 17. A composition according to claim 1wherein said viscosity controlling agent is tetra pentyl ammoniumbromide, tetra butyl ammonium bromide, diethylene glycol butyl ether,diethylene glycol methyl butyl ether, dipropylene glycol butyl ether,dipropylene glycol methyl butyl ether, butanol, isobutanol, pentanol,isopentilic alcohol, benzyl alcohol, and mixtures thereof.
 18. Acomposition according to claim 1 comprising from 0.001% to 10% byweight, of said viscosity controlling agent.
 19. A composition accordingto claim 18 comprising from 0.05% to 5% by weight, of said viscositycontrolling agent.